Antistain agents for photographic color materials



layers as described in Fischer U. S[ Patent Most of the compounds available for this purpose. 35

appear from the iollowing descriptionof our ina the development of a silver halide emulsion conone. or more color couplers. witha primary 55 Patented Apr. 13, 1954 ANTISTAIN AGENTS .FOR. rno'roenarmc COLOR MATERIALS Paul W. Vittum, Arnold Weissberger, and John R. Thirtle, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation' of New Jersey No Drawing. Application April 10, 1951,- o l Serial No. 220,336

9 Claims. (Cl. 95-6) 1 p 2 This inventionrelates to color photography and aromatic amino developing agent in the presence particularly to the prevention of color staining or of a compound having the formula fog in photographic emulsions containing color OH couplers. n The incorporation of color-forming components 5 (cmbvl c or couplers in silver halide emulsion layers is well known. These couplers are compounds such as phenolic hydroxyl compounds or compounds with reactive methylene groups which are capable OH of reacting with the oxidation products of priin which A is hydrogen. an alkyl group mary aromatic amino developing agents to proor duce indoaniline or azomethine dyes. The color R is an alkyl group Such as methyL ethyl lauryl C p s y be added directly to the emulsion hexadecyl, etc, or a substituted alkyl group such as hydroxyethyl, which may contain from 1 to 16 granted 1m 4 Or they may be or more carbon atoms, depending upon the use porated in a sep rate medium w c i to which the anti-stain agent is placed; soluble in the carrier for the sensitive silver B is or and halide as described in the Mannes and Godowsky n is 1 or U. S. Patent granted December 15, Where We refer in t claims" t an group, and Jeney and Patent 2,322,027 20 it is to be understood that we intend to include granted June 15, 1943. substituted alkyl groups.

In these p ss s in which e color upl rs The following examples illustrate the general are incorporated in the emulsion layers, the addiclass of compounds which w may tion oi -effective anti stainagents to the emul- L OH sion layers has-been found to confer instability to light upon some of the dye images formed in 0 the emulsion layers. Hydroquinone derivatives and other reducing agents such as ascorbic acid I have been used for this purpose. Because of the 1 instability conferred upon the dye images, it has 011 been found desirable to omit the anti-stain agent eenfi'ilaldmime from the emulsion and this necessitates the use N-oH of an anti-stain agent in the processing solutions.

2,fi-dihydroxyacetophenone oxime however, have interfered with color development by decreasing the amount of dye formed or have yielded developer solutions which are unstable.

It is, therefore, an object of the presentinvention to provide novel and useful anti-stain agents 40 3 0H for incorporation in silver halide emulsions containing color couplers. A further object is to -c provide suitable anti-stain agents for use in solu- \CHH" tions used to process such emulsions. A still further object is to provide anti-stain agents H which may be incorporated in photographic developer solutions for developing emulsions containing color couplers and which do not reduce the stability of such solutions. Other objects will 2,5-dihydroxylaurophenone oxime GentlIamlde vention.

These objects are accomplished by conducting NHCH:

N-methylgentisamide N- (B-hydroxyethyl)-gentisamide- NHCHaCHn OG 010mm;

N- (B-lauroyloxyethyl) -gentisamide N- (n-hexadecyl) -gentisamide N,N-dimethylgentisamide- Methyl gentisate Lauryl gentisate Ethyl [3- (2,5-dihydroiryphenyl) -propionate Lauryl B- (2,5-diliydroxyphenyl) -propionate CH2OHO B-(2,5-dihydroxyphenyl)-propionamide -oH;oH2o

NHCmHa:

N-(n-heziadecyl)-2,5-dihydroxy phenylpropionamide Compounds 1, 2, 4, 5, 6, 9, 10, 12 and 14 are designed for use as anti-stain agents to be applied during processing, that is, for treating the emulsion'at any stage not later than development. They may be incorporated'in the developing solution itself or in a pre-bath. Compounds 3, '7, 8, 11, 13 and 15 are suitable for incorporation in the emulsion layer during manufacture; In either case, the anti-stain agent will be present in the emulsion layer during color-forming developmentand'it is essential that the development of the emulsion'layer with the color'developing agent takesplace'inthepresenee of the'antistain agent. When the anti-stain agent isincorporated in the developer or in apre-bath; it diffuses into' the emulsion layer and is present in the'emulsion layer at the timezofdevelopment of the colored image.

The following example illustrates a developer solution useful for processing a multi-layer mate rial containing color couplers.

Example 1 2-amino-5-diethylaminotoluene hydrochloride g 3 Sodium sulfite (anhydix) g 4 Sodium carbonate (anhydn) g 20. Potassium bromide g 1 Gentisaldoxime g 0.5. 6-nitrobenzimidazole nitrate g 003 'Water cc 1000 The following example illustrates a pre-bath which may be used for two minutes immediately preceding color forming development to. secure the advantages of our invention.

Example 2 Sodium sulfite (anhydn) g f5 Potassium bromide g' '5 Gentisamide -1 g 1 Water 1 cc-.. 1000 The following example illustrates the incorporation of the anti-stain agent in an emulsion layer. I

Example 3' One gram of the coupler. N-l4-(benzoy1acetamino) -benzene-sulfonyll -N (y-phenylpropyl) p-toluidine and 0.1 gram of the'anti stain agent N-(n-liexadecyl) gentisamide were dissolved at C. in 3 cc. of di-n-butylphthalate. 'This hot' solution was poured with stirring into a solution" containing 18 cc. of10-% gelatin, 21c. of water, and 2 cc. of 10% Alkanol B (sodium triisopropylnaphthalene sulfonate). The whole mixture wasthen passed several'timesthrough a colloidmill and the resulting finedispersion wasadded. at 40 C. to 50 cc. of amelt'ed positire-type emulsion. The mixture was then coated on a support in the normal manner and Compound 4 was prepared as follows J. A. C. S.,

on DB (3-0 0,011, N113 Q'oorm,

OH OH Compound 5 can be prepared by the reaction of methyl gentisate (compound 10) with methylamine:

OH OH colon, GENE, CONH;

] H OH Compound 6 was prepared according to U. S. Patent 2,463,462 (1949). 7

Compound 7 can be synthesized as follows:

CONHOH'OH'OH 01111230 0o com CHzCH2C O OH K2520 connomcmooocun Compound 8 was prepared as follows:

- ocolclm on n O n a I Q oicolclm 041051 Pot --r OCOzCzHu OCOzCaHs 000202115 @42001 mcuHuNHi @CONHCuHas-n KOH OCOzCaHi OCOzCzHs 0 ON H C mHn-n Compound 9 can be prepared by the reaction of methyl gentlsate with dimethylamine:

OH OH I OH OH Compound 10 was prepared according to Ann.,

1 Compound ll'was prepared as follows:

Compound 12 can be prepared as follows: on OH -CH:CH2C O OH 02116011 CHzCHaC O O C2H Catalyst Compound 3 can b prepared like compound 12 by using dodecyl alcohol for the esterification. c .t V 7 R cinema 01H WCH'HHH omorno OizH25-Il Catalyst on a I we 1 Compound 14 can be prepared from compound 12 by reaction ofthe latter with ammonia.

on OH Oil?) 1110 0101315 NH cmomocnm OH OH compound l'dcanbe prepared from compound 12 by reaction of the latter with n-hexadecylifiine"or by aseries of 'reacticns such" as those described for compound 8.

CHzCHaCOaCzHt mOuHuNH *developed by reversal to form a colored image.

Our agents are particularly useful with sensitive materials coatedon papei' s'upports', where it is especially important to reduce the minimum or fog densities. This applies both to negativedeveloped paper and to reversal paper and transparency materials.

It will be understood that the examples and modifications 'disclosed 'herein are by way of example only and that our invention is to be taken as limited only by the scope of the appended claims.

I; In aprocess of'color photo'graphyfthemeth- 0d of preventing color stain in a photographic silver halide emulsion having a non-diffusing color coupler therein, which comprises exposing said'emulsion and developing it with a'p'rimary aromatic amino developing agent in the presence of a compound having the formula:

I OH

where A represents an alkyl radical- 2; In a process of color pho'togralphyfthe meth- "od "bf preventing-color photog'ra'p'hlc silver halideemulsion" having a non-diffusing ""cmor coupler-' therein; which comprises exposing -"said emulsion' and' developing it with a primary aromatic amino developing agent in the presence of a 'com'pound haiving the formula:

CHzCHzC ONHCit u-n n- C IOHSSNHB then K OH CHaCHzCO C1 OCOzCzHs aromatic "amino' developing agent inthe presence of acom'pound having the formula:

where A represents an alkylamino group.

4. In a process of color photography, the meth- 06. of preventing color stainson color images produced in a silver halide emulsion containing a color coupler, by development of saidemulsion with a primary aromatic amino developing agent, and treating said emulsion at a stage not later than development, with a solution of a compound having the formula:

where A is selected from the class consisting of hydrogen, R, --NI-I2, -NHR, NR2 and OR; B. is an alkyl group of less than 11 carbon atoms; B is selected from the class consisting of =NOH and =0; and n is a positive integer from 1 to 2.

5. The method of preventing the formation of stain in a photographic silver halide emulsion having a non-diffusing coupler compound therein, which comprises developing said emulsion after exposure, with a solution of a primary aromatic amino developing agent containing gentlsaldoxl'mc,

6. The method of preventing the formation of stain in a photographic silver halide emulsion having a non-difiusing coupler compound there in, which comprises developing said emulsion after exposure, with a solution of a primary aromatic amino developing agent containing gentisamide.

7. The method of preventing the formation of stain in a photographic silver halide emulsion having a non-diffusing coupler compound therein, which comprises developing said emulsion after exposure, with a solution of a primary aromatic amino developing agent containing N-(B- hydroxyethyl) -gentisamide.

8. A color-forming photographic silver halide emulsion having a non-diffusing color coupler incorporated therein, and containing 2,5-dihydroxylaurophenone oxime as an anti-stain agent.

10 9. A color-forming photographic silver halide emulsion having a, non-difiusing color coupler incorporated therein, and containing N-n-hexadecylgentisamide as an anti-stain agent.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date U 2,301,387 Evans et a1 Nov. 10., 1942 2,360,290 Vittum et a1 Oct. 10, 1944 2,384,658 Vittum Sept. 11, 1945 2,403,721 Jelley et a1. July 9, 19 6 FOREIGN PATENTS 15 Number Country Date 501,040 Great Britain May 10, 1937 545,732 Great Britain June 10, 1942 

1. IN A PROCESS OF COLOR PHOTOGRAPHY, THE METHOD OF PREVENTING COLOR STAIN IN A PHOTOGRAPHIC SILVER HALIDE EMULSION HAVING A NON-DIFFUSING COLOR COUPLER THEREIN, WHICH COMPRISES EXPOSING SAID EMULSION AND DEVELOPING IT WITH A PRIMARY AROMATIC AMINO DEVELOPING AGENT IN THE PRESENCE OF A COMPOUND HAVING THE FORMULA: 